Ortho-substituted benzyl esters of cyclopropanecarboxylic acids

ABSTRACT

Ortho-substituted benzyl esters of cyclopropanecarboxylic acids I ##STR1## where X is N or CH and A is one of the following cyclopropane radicals: ##STR2## where R 1  is CN, C 2  -C 8  -alkyl, CF 3 , C 3  -C 8  -alkenyl, (C 1  -C 4  -alkoxycarbonyl, unsubstituted or substituted phenyl-C 1  -C 6  -alkyl or phenyl-C 3  -C 6  -alkenyl, ethoxyphenyl, 2- or 3-bromophenyl, 2- or 4-trifluoromethylphenyl, 2,4- or 2,6-difluorophenyl, 2-fluoro-6-chlorophenyl, 2,4- or 2,6-dimethylphenyl, 2,3,6-trichlorophenyl or trimethylsilyl, R 2  is H or halogen, R 3  is unsubstituted or substituted phenyl, R 4  is CH 3  or halogen and Hal is halogen, with the proviso that X is CH when R 1  is CF 3  or trimethylsilyl, are suitable as fungicides and for controlling pests.

This application is a continuation of application Ser. No. 08/037,538,filed on Mar. 26, 1993, now abandoned, which is a continuation of Ser.No. 07/708,770 filed May 28, 1991 now abandoned.

The present invention relates to novel orthosubstituted benzyl esters ofcyclopropanecarboxylic acids of the general formula I ##STR3## where Xis nitrogen or ═CH-- and A is one of the following cyclopropaneradicals: ##STR4## where R¹ is cyano, C₂ -C₈ -alkyl, trifluoromethyl, C₃-C₈ -alkenyl, trimethylsilyl, C₁ -C₄ -alkoxycarbonyl, phenyl-C₁ -C₆alkyl or phenyl-C₃ -C₆ -alkenyl, where each aromatic moiety mayfurthermore carry 1-5 halogen atoms or up to 3 of the followingsubstituents: C₁ -C₆ -alkyl, partially or completely halogenated C₁ -C₆-alkyl or C₁ -C₆ -alkoxy, ethoxyphenyl, 2-bromophenyl, 3-bromophenyl,2-trifluoromethyiphenyl, 4-trifluoromethylphenyl, 2,4-difluorophenyl,2,6,-difluorophenyl, 2-fluoro-6-chlorophenyl, 2,4-dimethylphenyl,2,6-dimethylphenyl or 2,3,6-trichlorophenyl,

R² is hydrogen or halogen,

R³ is phenyl which may carry 1-5 halogen atoms or up to 3 of thefollowing substituents: C₁ -C₆ -alkyl, partially or completelyhalogenated C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy,

R⁴ is methyl or halogen and

Hal is halogen,

with the proviso that X is ═CH-- when R¹ is trifluoromethyl ortrimethylsilyl.

The present invention furthermore relates to a process for thepreparation of these compounds, their use as fungicides and forcontrolling pests, and fungicities and pesticides which contain thesecompounds as active substances.

EP-A 310 954 and EP-A 354 571 disclose, intel alia, fungicidalortho-substituted benzyl esters cyclopropanecarboxylic acids which areof the same as the compounds I and whose cyclopropane ring is stitutedor methyl- or dichloro-substituted or carries a phenyl radical havingvarious substituents. Furthermore, EP-A 354 571 discloses, inter alia,2-[1-trifluoromethylcyclopropylcarbonyloxymethyl]-phenyl-and2-[1-trimethylsilylcyclopropylcarbonyloxymethyl]-phenylglyoxylicacid methyl ester O-methyloxime. The stated publications do not discloseany insecticidal activity.

It is an object of the present invention to provide novelortho-substituted benzyl esters of cyclopropanecarboxylic acids.

We have found that this object is achieved by the ortho-substitutedbenzyl esters of cyclopropanecarboxylic acids of the formula I which aredefined at the outset.

In the novel compounds I, the substituents have the following specificmeanings:

R¹ is cyano;

branched or straight-chain C₂ -C₈ -alkyl, in particular C₂ -C₆ -alkyl,such as methyl, ethyl, isopropyl, n-butyl, tertbutyl, n-pentyl,isopentyl or neopentyl;

branched or straight-chain C₃ -C₆ -alkenyl, in particular C₃ -C₆-alkenyl, such as prop-2-enyl, 1-methylprop-2-enyl, but-2-enyl,3-methylbut-2-enyl or 2-methylprop-2-enyl; C₁ -C₄ -alkoxycarbonyl, inparticular methoxycarbonyl or ethoxycarbonyl;

phenyl-C₁ -C₆ -alkyl or phenyl-C₃ -C₆ -alkenyl, in particular phenyl-C₁-C₄ -alkyl or phenyl-C₃ - or -C₄ -alkenyl, such as benzyl,2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 3-phenylallyl or4-phenylbut-2-enyl, where each aromatic moiety may furthermore carry 1-5halogen atoms, such as fluorine, chlorine or bromine, or up to 3 of thefollowing substituents:

branched or straight-chain C₁ -C₆ -alkyl, in particular C₁ -C₄ -alkyl,such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl ortert-butyl, partially or completely halogenated, branched orstraight-chain C₁ -C₆ -alkyl, in particular C₁ -C₄ -alkyl, such asdifluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl or2-chloro-1,1,2-trifluoroethyl, or branched or straight-chain C₁ -C₆-alkoxy, in particular C₁ -C₄ -alkoxy, such as methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy or tert-butoxy;

ethoxyphenyl, such as 2-, 3- or 4-ethoxyphenyl;

2- or 3-bromophenyl;

2- or 4-trifluoromethylphenyl;

2,4- or 2,6-difluorophenyl;

2-fluoro-6-chlorophenyl;

2,4- or 2,6-dimethylphenyl;

2,3,6-trichlorophenyl or trimethylsilyl or trifluoromethyl;

R² is hydrogen or halogen, such as fluorine, chlorine or bromine;

R³ is phenyl which may carry 1-5 halogen atoms, such as fluorine,chlorine or bromine, or up to 3 of the following substituents:

branched or straight-chain C₁ -C₆ alkyl, in particular C₁ -C₄ -alkyl,such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl ortert-butyl,

partially or completely halogenated, branched or straight-chain C₁ -C₆alkyl, in particular C₁ -C₄ -alkyl, such as difluoromethyl,trifluoromethyl, chloromethyl, trichloromethyl, pentafluoroethyl or2-chloro-1,1,2-trifluoroethyl, or

branched or straight-chain C₁ -C₆ alkoxy, in particular C₁ -C₄ -alkoxy,such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy,

preferred groups being 2-, 3- and 4-fluorophenyl, 2-, 3- and4-chlorophenyl, 2-, 3- and 4-bromophenyl, 2-, 3- and 4-methylphenyl,4-tert-butylphenyl, 2-, 3- and 4-trifluoromethylphenyl, 2-, 3- and4-methoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-difluorophenyl,2,6-difluorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl,2,6-dichlorophenyl, 2-fluoro-6-chlorophenyl, 2,3,6-trichlorophenyl,2,4-, 3,4- and 2,6-dimethylphenyl, 2,4-, 3,4- and 2,6-dimethoxyphenyland 3,4-diethoxyphenyl;

R⁴ is methyl or halogen, such as fluorine, chlorine or bromine, and

Hal is halogen, such as fluorine, chlorine or bromine.

Particularly suitable compounds I are shown in Table 1. Compounds Iawhose cyclopropane ring is monosubstituted by the following radicalsR^(1') are preferred:

cyano;

C₂ -C₄ -alkyl, such as ethyl, n-propyl, isopropyl or tertbutyl;

trifluoromethyl;

C₃ - or C₄ -alkenyl, such as prop-2-enyl or but-2-enyl;

methoxycarbonyl or ethoxycarbonyl;

phenyl-C₁ -C₄ -alkyl or phenyl-C₃ - or -C₄ -alkenyl, where each aromaticmoiety may furthermore carry one of the following substituents:

halogen, such as fluorine, chlorine or bromine, or methyl, in particularbenzyl, 3- or 4-fluorobenzyl, 3- or 4-chlorobenzyl, 4-bromobenzyl,3-methylbenzyl, 3-(4-fluorophenyl)-propyl, 3-(4-chlorophenyl)-propyl,3-(4-fluorophenyl)-prop-2-enyl or 3-(4-chlorophenyl)-prop-2enyl;

2-bromophenyl;

2,4- or 2,6-difluorophenyl;

2-fluoro-6-chlorophenyl;

2,3,6-trichlorophenyl and trimethylsilyl.

If R^(1') is phenylalkenyl, the E configuration at the double bond isparticularly preferred.

The novel compounds I may be obtained as E/Z isomer mixtures in thepreparation, owing to the substituent --C(COOCH₃)═X--OCH₃ ortho to thebenzyl moiety. The isomers can, if desired, be separated by theconventional methods, for example by crystallization or chromatography.Compounds having the E configuration are particularly preferred.

In compounds I whose cyclopropane ring carries various substituents inthe 2- and 3-positions, two configurations are also possible in the1-position of the cyclopropane ring (which position carries the benzylester group). If the cyclopropane ring carries a methyl group in the2-position (compounds Ib of Table 2), particularly preferred compoundsare those in which the methyl group is in the trans position withrespect to the benzyl ester group of the parent structure.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids Iare obtainable in various ways, preferably by converting acyclopropanecarboxylic acid II with a base in a conventional manner, inan inert solvent, such as ethanol, into the carboxylate anion andreacting this anion with an ortho-substituted benzyl compound III (cf.Synthesis 1975, 805): ##STR5##

L is a nucleophilic leaving group, in particular sulfonyl, such asmethanesulfonyl, trifluoromethylsulfonyl, p-toluenesulfonyl orp-bromophenylsulfonyl, or a methylsulfate radical, particularlypreferably halogen, such as chlorine, bromine or iodine.

Particularly suitable bases are alkali metal hydroxides, such as sodiumhydroxide and potassium hydroxide, and triethylamine.

The reaction of the carboxylate anion with the benzyl compound III isadvantageously carried out in a solvent or diluent, such as acetone,acetonitrile, dimethyl sulfoxide, dioxane, dimethylformamide,N-methylpyrrolidone, N,N'-dimethylpropyleneurea or pyridine or, using aphase transfer catalyst, in a 2-phase system consisting of water and ahydrocarbon, such as carbon tetrachloride.

Examples of suitable phase transfer catalysts are trioctylpropylammoniumchloride and cetyltrimethylammonium chloride (cf. Synthesis 1974, 867).

Advantageously, all starting compounds are used in a roughlystoichiometric ratio, but an excess of one or other component, forexample of up to 10%, may also be advisable in some cases.

In general, the reaction temperature is from 0° C. to the boiling pointof the solvent, preferably from 20° to 130° C.

Since the reaction is not pressure-dependent, it is advantageouslycarried out at atmospheric pressure.

The cyclopropanecarboxylic acids II are known or can be prepared byknown processes [cf. for example Synthesis (1987), 738; Zh. Org. Khim 16(1980), 2086; J. Am. Chem. Soc. 106 (1984), 6642; Chem. Ber. 116 (1983),3895; Helv. Chim. Acta 69 (1986), 1655; Chem. Bet. (1986), 3694; Chem.Letters (1989), 475; J. Organometal. Chq. 46 (1972), 73; Gazz. Chim.Ital. 100 (1970), 566; J. Org. Chem. 48 (1983), 2472 and J. Org. Chem.47 ( 1982 ), 893].

The ortho-substituted benzyl compounds III (where X is CH and L ischlorine or bromine) are likewise known or can be prepared by knownprocesses (cf. for example DE-A 35 19 280, DE-A 35 45 318 and DE-A 35 45319).

For example, the ortho-substituted benzyl bromide III (where X is CH andL is bromine) can be obtained by brominating the correspondingortho-substituted toluene IV with N-bromosuccinimide (cf. Angew. Chem.71 (1959), 349): ##STR6##

The ortho-substituted toluene IV can be prepared by a method in which,for example, a hydroxymethylene derivative Va, which is in equilibriumwith the corresponding formyl derivative Vb, is alkylated in thepresence of a base, such as potassium carbonate: ##STR7## Z ismethylsulfate, chloride, bromide or iodide.

Examples of suitable alkylating agents are dimethyl sulfate and methyliodide, chloride and bromide.

The reaction is usually carried out in an inert solvent, for example inacetone.

The reaction temperature is in general from 20° to 60° C.

The hydroxymethylene derivative Va is obtainable, i5 for example, bybase-catalyzed reaction of methyl 2-methylphenylacetate with methylformate in an inert solvent, such as diethyl ether or tetrahydrofuran,and sodium hydroxide, for example, can be used as the base (cf. Ann.Chem. 424 (1921), 214).

Ortho-substituted benzyl compounds III, where X is nitrogen and L ischlorine or bromine, are obtainable by various methods, advantageouslyby halogenating 2-methylphenylglyoxylic acid methyl esters O-methyloximeVI. ##STR8##

Chlorine or bromine in an inert solvent, e.g. tetrachloromethane, orhalogenating agents, such as N-chloro- and N-bromosuccinimide [cf.Angew. Chem. 71 (1959), 349], in CCl₄ can be used for the halogenation.When elemental chlorine or bromine is used, it is advisable to carry outthe reaction photochemically by exposure to sunlight.

The 2-methylphenylglyoxylic acid methyl ester O-methyloxime VI disclosedin DE-A 36 23 921 is advantageously obtainable from methyl2-methylphenylglyoxylate by reaction with O-methylhydroxylaminehydrochloride or hydroxylamine hydrochloride, the primary product inthis case being an oxime, which is then treated with a methylatingagent, such as methyl chloride, methyl bromide, methyl iodide ordimethyl sulfate.

In a possible process variant for the preparation of the benzylcompounds III (where Y is nitrogen and L is chlorine or bromine), themethyl 2-methylphenylglyoxylate VII disclosed in DE-A 36 23 921 is firsthalogenated by one of the methods described above and the product isconverted into the corresponding oxime: ##STR9##

The ortho-substituted benzyl compounds III where the leaving group L isa p-toluenesulfonate, p-bromophenylsulfonate, methanesulfonate ortrifluoromethanesulfonate radical can be prepared from the benzylcompounds III where L is chlorine or bromine by reaction withp-toluenesulfonic acid, p-bromophenylsulfonic acid, methanesulfonic acidor trifluoromethanesulfonic acid.

The reaction is advantageously carried out in a solvent or diluent, e.g.dimethylformamide, in the presence of a base, e.g. potassium carbonate.

The reaction temperature is in general from 20° to 130° C.

In a process variant, the benzyl compounds III (where L is chlorine orbromine) are reacted with the alkali metal salts, preferably the sodiumor potassium salts, of the sulfonic acids in the inert solvent.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids Iare suitable as fungicides and for controlling pests.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids Ihave excellent activity against a broad spectrum of phytopathogenicfungi, in particular from the class consisting of the Ascomycetes andBasidiomycetes. Some of them have systemic activity and can be used asfoliage and soil fungicides.

They are particularly important for controlling a large number of fungion various crops, such as wheat, rye, barley, oats, rice, corn, grass,cotton, soybean, coffee, sugar cane, grapevines, fruit trees,ornamentals and vegetable plants, such as cucumbers, beans andcucurbitaceae, and on the seeds of these plants.

They are particularly suitable for controlling the following plantdiseases:

Erysiphe graminis (powdery mildew) in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbitaceae,

Podosphaera leucotricha on apples,

Uncinula necator on grapevines,

Puccinia species on cereals,

Rhizoctonia species on cotton and lawns,

Ustilago species on cereals and sugar cane,

Venturia inaequalis (scab) on apples, Helminthosporium species oncereals,

Septoria nodorum on wheat,

Botrytis cinerea (gray mold) on strawberries and grapevines,

Cercospora arachidicola on peanuts,

Pseudocercosporella herpotrichoides on wheat and barley,

Pyricularia oryzae on rice,

Phytophthora infestans on potatoes and tomatoes,

Fusarium and Verticillium species on various plants,

Plasmopara viticola on grapevines and

Alternaria species on vegetables and fruits.

The compounds are used for treating the fungi or the plants, seeds ormaterials to be protected from fungal attack or the soil with afungicidal amount of the active ingredients. Application is effectedbefore or after infection of the materials, plants or seeds by thefungi.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids Iare furthermore suitable for controlling pests from the class consistingof insects, arachnids and nematodes. They can be used as pesticides incrop protection, in the hygiene and veterinary sectors and for theprotection of stored materials.

The insect pests include, from the order of the butterflies(Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabamaargillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographagamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana,Cheimatobia brumata, Choristoneura fumiferana, Choristoneuraoccidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini,Diaphania nitidalis, Diatraea grandiosella, Earias insulana,Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana,Feltia subterranea, Galleria mellonella, Grapholita funebrana,Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothiszea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeutamalinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygmaexigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletisblancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar,Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestrabrassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea,Pectinophora gossypiella, Peridroma saucia, Phalera bucephala,Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae,Plathypena scarbra, Plutella xylostella, pseudoplusia includens,Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerelella,Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis,Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana,Trichoplusia ni and Zeiraphera canadensis;

from the order of the beetles (Coleoptera), for example Agrilussinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallussolstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum,Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchusrufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassidanebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchusnapi, Chaetocnema tibiails, Conoderus vespertinus, Crioceris asparagi,Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera,Eiplachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis,Hylobius abietis, Hypera brunneipennis, HArpera postica, Ipstypographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata,Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis,Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha,Onlema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedoncochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phylloperthahorticola, Phyllotreta nemorum, Phyllotreta striolata, PopilliaJaponica, Sitona lineatus and Sitophilus granaria.;

from the order of the Diptera, for example Aedes aegypti, Aedes vexans,Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomyabezziana, Chrysomya hominivorax, Chrysomya macellaria, Contariniasorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae,Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilusintestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosisequestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae,Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata,Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscinastabulans, Oestrus ovis, Oscinella firt, Pegomya hysocyami, Phorbiaantiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi,Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipulapaludosa;

from the order of the Thysanoptera, for example Franklinleila fusca,Franklinleila occidentalis, Franklinleila tritici, Scirtothrips citri,Thrips oryzae, Thrips palmi and Thrips tabaci;

from the order of the Hymenoptera, for example Athalia rosae, Attacephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampatestudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsisinvicta; from the order of the Heteroptera, for example Acrosternumhilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus,Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris,Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezaraviridula, Piesma quadrata, Solubea insularis and Thyanta perditor;

from the order of the Homoptera, for example Acyrthosiphon onobrychis,Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphissambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii,Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola,Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae,Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophiumdirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigusbursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mall,Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphismala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa,Trialeurodes vaporariorum and Viteus vitifolii;

from the order of the Isoptera, for example Calotermes flavicollis,Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis;

from the order of the Orthoptera, for example Acheta domestica, Blattaorientalis, Blattella germanica, Forficula auricularia, Gryllotalpagryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplusfemurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplusspretus, Nomadacris septemfasciata, Priplaneta americana, Schistocercaamericana, Schistocerca peregrina, Stauronotus maroccanus and Tachycinesasynamorus;

from the class of the Arachnoidea, for example Acarina, such asAmhlyomma americanum, Amglyomma variegatum, Argas persicus, Boophilusannulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpusphoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychuscarpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodesrubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychuspilosus, Permanyssus gallinae, Phyllocaptrata oleivora,Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus,Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus,Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius andTetranychus urticae;

from the class of the nematodes, for example root gall nematodes, e.g.Meloidogyne hapla, Meloidogyne incognita and Meloidogyne Javanica,cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae,Heterodera glycinae, Heterodera schatii, Heterodera triflolii, and stemand leaf borers, e.g. Belonolaimus lonicaudatus, Ditylenchus destructor,Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidoruselongatus, Radopholus similis, Rotylenchus robustus, Trichodorusprimitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius,Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatusand Pratylenchus goodeyi.

The active ingredients can be converted into the conventionalformulations, such as solutions, emulsions, suspensions, dusts, powders,pastes and granules. The application forms depend on the intended uses;they should in any case ensure fine and uniform distribution of theortho-substituted benzyl ester of a cyclopropanecarboxylic acid. Theformulations are prepared in a known manner, for example by extendingthe active ingredient with the solvents and/or carriers, if requiredwith the use of emulsifiers and dispersants; where water is used as adiluent, other organic solvents may also be employed as auxiliarysolvents.

For the preparation of directly sprayable solutions, emulsions, pastesor oil dispersions, mineral oil fractions having a medium to highboiling point, such as kerosene or diesel oil, and coal tar oils andoils of vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons, e.g. benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof,methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride,cyclohexanol, cyclohexanone, chlorobenzene, isophorone and stronglypolar solvents, e.g. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water, are suitable.

Aqueous application forms can be prepared from emulsion concentrates,pastes or wettable powders (spray powders, oil dispersions) by addingwater. For the preparation of emulsions, pastes or oil dispersions, thesubstances, as such or dissolved in an oil or solvent, can behomogenized in water by means of wetting agents, adhesives, dispersantsor emulsifiers. However, concentrates which consist of active substance,wetting agents, adhesives, dispersants or emulsifiers and possibly asolvent or oil and which are suitable for dilution with water can alsobe prepared.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid and dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ethers, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof naphthalenesulfonic acid with phenol and formaldehyde,polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol,octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenylpolyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, ligninsulfite wasteliquors and methylcellulose.

Powders, broadcasting agents and dusting agents can be prepared bymixing or milling the active substances together with a solid carrier.

The formulations contain in general from 0.01 to 95, preferably from 0.1to 90, % by weight of the active ingredient. The active ingredients areused in a purity of from 90 to 100%, preferably from 95 to 100%(according to NMR spectrum).

Examples of such formulations are:

I. a solution of 90 parts by weight of compound No.

3 and 10 parts by weight of N-methyl-α-pyrrolidone, which solution issuitable for use in the form of very small drops;

II. a mixture of 20 parts by weight of compound No. 4, 80 parts byweight of xylene, 10 parts by weight of the adduct of from 8 to 10 molesof ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 partsby weight of the calcium salt of dodecylbenzenesulfonic acid, 5 parts byweight of the adduct of 40 moles of ethylene oxide with 1 mole of castoroil; by finely distributing the solution in water, a dispersion isobtained;

III. an aqueous dispersion of 20 parts by weight of compound No. 5, 40parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20parts by weight of the adduct of 40 moles of ethylene oxide with 1 moleof castor oil;

IV. an aqueous dispersion of 20 parts by weight of compound No. 6, 25parts by weight of cyclohexanol, 65 parts by weight of a mineral oilfraction boiling within a range from 210° to 280° C. and 10 parts byweight of the adduct of 40 moles of ethylene oxide with 1 mole of castoroil;

V. a mixture milled in a hammer mill and consisting of 80 parts byweight of compound No. 7, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of ligninsulfonic acid obtained from a sulfite waste liquor and 7parts by weight of silica gel powder; by finely distributing the mixturein water, a spray liquor is obtained;

VI. an intimate mixture of 3 parts by weight of compound No. 15 and 97parts by weight of finely divided kaolin; this dusting agent contains 3%by weight of the active ingredient;

VII. an intimate mixture of 30 parts by weight of compound No. 103, 92parts by weight of silica gel powder and 8 parts by weight of liquidparaffin, which was sprayed onto the surface of this silica gel; thisformulation imparts good adhesion to the active ingredient;

VIII. a stable aqueous dispersion of 40 parts by weight of compound No.109, 10 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate, 2 parts by weight of silica gel and48 parts by weight of water, which dispersion can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of compound No. 177,2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 20 parts by weightof the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil.

Granules, for example coated, impregnated and homogeneous granules, canbe prepared by binding the active ingredients to solid carriers.Examples of solid carriers are mineral earths, such as silica gel,silicas, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesiumsulfate, magnesium oxide, milled plastics, fertilizers, e.g. ammoniumsulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetableproducts, such as cereal meal, ground bark, woodmeal and nutshell meal,cellulose and other solid carriers.

The active ingredient concentrations in the ready-to-use formulationscan be varied within wide ranges.

Very generally, the agents contain from 0.0001 to 95, preferably from0.01 to 90, % by weight of active ingredient.

Formulations containing more than 95% by weight of active ingredient canbe successfully applied by the ultralow volume method (ULV), and it iseven possible to use the active ingredient without additives.

In the case of fungicides, the application rates are from 0.02 to 3 kgof active ingredient per ha, depending on the type of effect desired.The novel compounds can also be used in material protection (woodpreservation), for example against Paecilomyces variotii.

In seed treatment, amounts of active ingredient of from 0,001 to 50 g,preferably from 0.01 to 10 g, per kilogram of seed are generallyrequired.

The application rate of active ingredient for controlling insects isfrom 0.02 to 10, preferably from 0.1 to 2.0, kg/ha under open airconditions.

The novel agents in these application forms may be present together withother active ingredients, for example with herbicides, insecticides,growth regulators, fungicides or fertilizers. These agents can be addedto the novel agents in a weight ratio of from 1:10 to 10:1, if necessaryalso immediately before use (tank mix). Mixing with fungicides orinsecticides results in an extension of the action spectrum in manycases.

The agents or the ready-to-use formulations prepared therefrom, such assolutions, emulsions, suspensions, powders, dusts, pastes or granules,are applied in a known manner, for example by spraying, atomizing,dusting, broadcasting, dressing or pouring.

PREPARATION EXAMPLES Example 1 (Compound No. 3 in Table 1) Methylalpha-{2-[1-(n-propyl)-cyclopropylcarbonyloxymethyl]-phenyl}-beta-methoxyacrylate##STR10##

A solution of 3.5 g (27 mmol) of 1-n-propylcyclopropanecarboxylic acidand 1.5 g (27 mmol) of potassium hydroxide in 75 ml of ethanol wasstirred for 2 hours at 20° C. Thereafter, the precipitated potassiumsalt was separated off, washed with 100 ml of diethyl ether andsuspended in 50 ml of dimethylformamide. 5.7 g (20 mmol) of methylalpha-(2-bromomethylphenyl)-betamethoxyacrylate were added to thissuspension and the mixture was then heated for 2 hours at 90° C. Aftercooling to 20° C., the mixture was hydrolyzed with 50 ml of water. Theproduct was then extracted with diethyl ether and isolated in aconventional manner. Purification was carried out by chromatographyusing silica gel as the adsorbent and cyclohexane as the mobile phase.Yield: 66%; mp.: 62°-64° C.

Intermediate 1a

tert-Butyl 1-allylcyclopropanecarboxylate ##STR11##

A solution of 34.1 g (0.24 mol) of tert-butyl cyclopropanecarboxylate in25 ml of tetrahydrofuran was added dropwise at -70° C. to a mixture of33.6 ml (0.24 mol) of diisopropylamine, 150 ml of a 1.5 molar solutionof n-butyllithium in n-hexane (=0.24 mol of butyllithium) and 100 ml oftetrahydrofuran. Stirring was carried out for 3 hours at -70° C., afterwhich a solution of 27.8 g (0.23 mol) of allyl bromide in 25 ml oftetrahydrofuran was added dropwise. Thereafter, the reaction mixture wasstirred for a further 2 hours at -70° C. and then for 12 hours at 20° C.After hydrolysis with 50 ml of saturated aqueous ammonium chloridesolution and after phase separation, the organic phase was worked up ina conventional manner to obtain the product. The crude product waspurified by distillation. Yield: 61%, bp.: 86°-88° C. at 30 mbar;colorless oil.

Intermediate 1b

tert-Butyl 1-n-propylcyclopropanecarboxylate ##STR12##

25.5 g (0.14 mol) of tert-butyl 1-allylcyclopropanecarboxylate,dissolved in 150 ml of tetrahydrofuran, were hydrogenated at 30° C. andat a hydrogen pressure of 10 bar, with the addition of 6 g of aluminawhich contained 0.5% by weight of palladium. After no further hydrogenwas absorbed (constant pressure), the solids were filtered off and thefiltrate was evaporated to dryness. The crude product was purified bydistillation. Yield: 87%; bp.: 89° C. at 36 mbar; colorless oil.

Intermediate 1c 1-n-Propylcyclopropanecarboxylic acid ##STR13##

A stirred mixture of 21.0 g (0.11 mol) of tertbutyl1-n-propylcyclopropanecarboxylate and 13.0 g (0.11 mol) oftrifluoroacetic acid was refluxed for 3 hours and then added to 20 ml ofdilute sodium hydroxide solution. After extraction of the byproductswith diethyl ether, the aqueous phase was acidified with dilutehydrochloric acid and again extracted with diethyl ether. This etherphase was then worked up in a conventional manner to obtain the product.Yield: 95%; colorless oil.

EXAMPLE 2 (compound No. 4 in Table 1)2-[1-(n-Propyl)-cyclopropylcarbonyloxymethyl]-phenylglyoxylic acidmethyl ester O-methyloxime ##STR14##

A mixture of 2.8 g (22 mmol) of 1-n-propylcyclopropanecarboxylic acid(prepared according to Example 1c), 1.3 g (23 mmol) of potassiumhydroxide and 50 ml of ethanol was stirred for 1 hour at 20° C.Thereafter, the precipitated potassium salt was separated off, washedwith 50 ml of diethyl ether and suspended in 100 ml ofdimethylformamide. 4.3 g (15 mmol) of 2-(bromomethyl)-phenylglyoxylicacid methyl ester O-methyloxime were added to this suspension and themixture was then heated for 2 hours at 100° C. After cooling to 20° C.,the mixture was hydrolyzed with 50 ml of water and worked up similarlyto Example 1 to obtain the product. Yield: 38%; mp. 56°-59° C.;colorless crystals.

Example 3 (Compound No. 5 in Table 1) Methylalpha-{2-[1-(allyl)-cyclopropylcarbonyloxymethyl]phenyl}-beta-methoxyacrylate##STR15##

A solution of 4.5 g (36 mmol) of 1-allylcyclopropanecarboxylic acid and2.2 g (39 mmol) of potassium hydroxide in 50 ml of ethanol was stirredfor 2 hours at 20° C. and then evaporated down. The residue was coveredwith a layer of diethyl ether, after which the resulting precipitate wasseparated off and washed with diethyl ether. Subsequent reaction of thepotassium salt of 1-allylcyclopropanecarboxylic acid in 50 ml ofN-methylpyrrolidone with 8.5 g (30 mmol ) of methyl alpha-(2-bromomethylphenyl)-beta-methoxyacrylate and purification of the endproduct were carried out similarly to Example 1. Yield: 40%; colorlessoil.

Intermediate 3a

1-Allylcyclopropanecarboxylic acid ##STR16##

24.0 g (0.13 mol) of tert-butyl 1-allylcyclopropanecarboxylate (preparedaccording to Example 1a) were reacted with 14.9 g (0.13 mol) oftrifluoroacetic acid similarly to Example 1c. Yield: 90%; colorless oil.

EXAMPLE 4 (Compound No. 6 in Table 1)

2-[1-(Allyl)-cyclopropylcarbonyloxymethyl]-phenylglyoxylic acid methylester O-methyloxime ##STR17##

2.3 g (18 mmol) of 1-allylcyclopropanecarboxylic acid (preparedaccording to Example 1c) were converted with 1.1 g (20 mmol) ofpotassium hydroxide into the potassium salt of1-allylcyclopropanecarboxylic acid similarly to Example 3, and said saltin 50 ml of dimethylformamide was reacted with 4.3 g (15 mmol) of2-(bromomethyl)-phenylglyoxylic methyl ester O-methyloxime. Yields: 84%;colorless oil.

EXAMPLE 5 (Compound No. 7 in Table 1) Methylalpha-{2-[1-(trifluoromethyl)-cyclopropylcarbonyloxymethyl]-phenyl}-beta-methoxyacrylate##STR18##

A solution of 10.0 g (55 mmol) of ethyl1-trifluoromethylcyclopropanecarboxylate and 3.4 g (61 mmol) ofpotassium hydroxide in 150 ml of ethanol was stirred for 4 hours at 40°C. and then evaporated down. The residue was covered with a layer ofdiethyl ether, after which the resulting precipitate was separated off,washed with diethyl ether and suspended in 100 ml of dimethylformamide.10.0 g (35 mmol) of methylalpha-(2-bromo-methylphenyl)-beta-methoxyacrylate were added to thissuspension and the mixture was then heated for 2 hours at 95° C. Aftercooling to 20° C., the mixture was hydrolyzed with 50 ml of water. Theproduct was then extracted with diethyl ether and isolated in aconventional manner.

The oily crude product was covered with a layer of pentane and wascrystallized by rubbing the wall of the vessel. Yield: 64%; mp.: 58°-60°C.; white crystals.

Intermediate 5a

Monoethyl cyclopropane-1,1-dicarboxylate ##STR19##

A solution of 53 g (285 mmol) of diethyl cyclopropane-1,1-dicarboxylateand 16.0 g (286 mmol) of potassium hydroxide in 300 ml of ethanol wasstirred for 3 hours at 20° C. and then evaporated to dryness. Theresidue was dissolved in 100 ml of water, after which byproducts wereextracted with 200 ml of methylene chloride. After the aqueous phase hadbeen acidified to pH 2 with dilute hydrochloric acid, the product wasextracted with 200 ml of methyl tert -butyl ether and isolated in aconventional manner. Purification was carried out by distillation.Yield: 83%; bp.: 99°-102° C. at 2.5 mbar; colorless oil.

Intermediate 5b

Ethyl 1-trifluoromethylcyclopropanecarboxylate ##STR20##

31.6 g (0.20 mol) of monoethyl cyclopropane-1,1-dicarboxylate, 126 g(1.16 mol) of sulfur tetrafluoride, 100 ml of dichloromethane and 1.5 g(75 mmol) of hydrogen fluoride were introduced at -70° C. into a 500 mlstirred autoclave which was lined with an alloy of 70% of nickel, 15% ofchromium and 15% of molybdenum. The mixture was heated for 48 hours at80° C. and the gaseous constituents were destroyed, after cooling theautoclave to 35° C., by passing them into a wash tower filled withpotassium hydroxide. The residue was dissolved in 100 ml ofdichloromethane. The solution was washed with 100 ml of saturated sodiumbicarbonate solution, after which the organic phase was dried withsodium sulfate and potassium fluoride and was separated into theindividual components by distillation. Yield: 76%; bp.: 141°-142° C.;oil.

Example 6 (Compound No. 8 in Table 1 )

Methylalpha-{2-[1-(trimethylsilyl)-cyclopropylcarbonyloxymethyl]-phenyl}-beta-methoxyacrylate##STR21##

A procedure similar to Example 3 was used and 4.5 g (28mmol) of1-trimethylsilylcyclopropanecarboxlic acid, dissolved in 80 ml ofethanol, were converted with 1.8 g (32 mmol) of potassium hydroxide intothe potassium salt of trimethylsilylcyclopropanecarboxylic acid, and thelatter was reacted with 5.7 g (20 mmol) of methylalpha-(2-bromomethylphenyl)-beta-methoxyacrylate at 100° C. Yield: 62%;colorless oil.

Intermediate 6a

1-Trimethylsilylcyclopropanecarboxylic acid ##STR22##

12.9 g (0.15 mol) of cyclopropanecarboxylic acid were added dropwise at-78° C. to a mixture of 42.0 ml (0.30 mol) of diisopropylamine, 200 mlof a 1.5 molar solution of n-butyllithium in n-hexane (=0.30 mol ofbutyllithium) and 150 ml of tetrahydrofuran, followed, after stirringfor 30 minutes, by the dropwise addition of 81.3 g (0.75 mol) oftrimethylchlorosilane at -78° C. Thereafter, the reaction mixture wasstirred for a further 30 minutes at 0° C. and was heated to 20° C., 150ml of methanol were then added and stirring was continued for a further30 minutes. Hydrolysis was effected with water, after which the organicphase was separated off and evaporated down. Colorless crystals wereobtained from the concentrated solution. Yields 38%; mp.: 124°-126° C.

Example 7 (Compound No. 11 in Table 1) Methyl alpha-{2-[1-(ethoxycarbonyl)-cyclopropylcarbonyloxymethyl]-phenyl}-beta-methoxyacrylate##STR23##

A method similar to Example 1 was used and 7.9 g (50 mmol) of monoethylcyclopropane-1,1-dicarboxylate (prepared according to Example 5a) wereconverted with 2.8 g (50 mmol) of potassium hydroxide into the potassiumsalt of monomethyl cyclopropane-1,1-dicarboxylate, and said salt wasthen reacted with 10 g (35 mmol) of methylalpha-[2-(bromomethyl)-phenyl]-beta-methoxyacrylate. The product waspurified by distillation. Yield: 66%; bp.: 220° C. at 0.3 mbar;colorless oil.

Example 8 (Compound No. 17 in Table 1) Methylalpha-{2-[1-(2,6-difluorophenyl)-cyclopropylcarbonyloxymethyl]-phenyl}-beta-methoxyacrylate##STR24##

A method similar to Example 1 was used and 12.8 g (65 mmol) of1-(2,6-difluorophenyl)-cyclopropanecarboxylic acid, dissolved in 60 mlof ethanol, were converted with 4.0 g (71 mmol) of potassium hydroxideinto the potassium salt of 2,6-difluorophenylcyclopropanecarboxylicacid, and said salt was then reacted, at 100° C., in 100 ml ofN-methylpyrrolidone, with 11.4 g (40 mmol) of methylalpha-(2-bromomethylphenyl)-betamethoxyacrylate. The resulting oilyproduct was covered with a layer of diisopropyl ether and wascrystallized by rubbing the wall of the vessel. Yield: 86%; mp.:108°-110° C.; white crystals.

Intermediate 8a

1-(2,6-Difluorophenyl)-cyclopropylnitrile ##STR25##

4.0 g of tetrabutylamonium chloride were added to a mixture of 30.6 g(0.20 mol) of 2,6-difluorobenzyl cyanide and 150.0 g (0.80 mol) of1,2-dibromoethane, and 150 ml of 50% strength sodium hydroxide solutionwere then added dropwise. Stirring was carried out for 5 hours at 60°C., after which hydrolysis was effected with ice water. The product wasextracted with diethyl ether from the resulting mixture and was isolatedin a conventional manner. Purification was carried out by chromatographyusing silica gel as the adsorbent and cyclohexane as the mobile phase.Yield: 52%; mp.: 56°-58° C.; colorless crystals.

Intermediate 8b

(2,6-Difluorophenyl)-cyclopropanecarboxylic acid ##STR26##

A suspension of 17.9 g (100 mmol) of1-(2,6-difluorophenyl)-cyclopropylnitrile in a mixture of 60 ml of icewater and 40 ml of concentrated sulfuric acid was refluxed for 4 hours.The mixture was cooled to 25° C., after which the resulting precipitatewas separated off, washed with water and dried. Yield=89%; mp.:150°-153° C.; colorless crystals.

Example 9 (Compound No. 18 in Table 1)2-[1-(2,6-Difluorophenyl)-cyclopropylcarbonyloxymethyl]-phenylglyoxylicacid methyl ester O-methyloxime ##STR27##

A method similar to Example 2 was used and 11.8 g (60 mmol) of1-(2,6-difluorophenyl )-cyclopropanecarboxylic acid, prepared accordingto Example 8b and dissolved in 60 ml of ethanol, were converted with 3.6g (64 mmol) of potassium hydroxide to the potassium salt of2,6-difluorophenylcyclopropanecarboxylic acid, and said salt was thenreacted, at 90° C., in 100 ml of N-methylpyrrolidone, with 13.3 g (47mmol) of 2-(bromomethyl)phenylglyoxylic acid methyl ester O-methyloxime.The resulting oily product was covered with a layer of diisopropyl etherand was crystallized by rubbing the wall of the vessel. Yield: 85%; mp.:122°-123° C.; white crystals.

Example 10 (Compound No. 29 in Table 1) Methylalpha-{2-[1-(4-fluorobenzyl)-cyclopropylcarbonyloxymethyl]-phenyl}-beta-methoxyacrylate##STR28##

A method similar to Example 3 was used and 6.3 g (32 mmol) of1-(4-fluorobenzyl)-cyclopropanecarboxylic acid were converted with 2.0 g(36 mmol) of potassium hydroxide into the potassium salt offluorobenzylcyclopropanecarboxylic acid, and said salt was then reactedat 100° C. with 6.3 g (22 mmol) of methylalpha-(2-bromomethylphenyl)-beta-methoxyacrylate. Yield: 54%; colorlessoil.

Intermediate 10a

tert-Butyl 1-(4-fluorobenzyl)-cyclopropanecarboxylate ##STR29##

34.1 g (0.24 mol) of tert-butyl cyclopropanecarboxylate were convertedinto a lithium complex similarly to Intermediate 1a and this complex wasreacted with 30.2 g (0.16 mol ) of 4-fluorobenzyl bromide. Purificationwas carried out by chromatography using silica gel as the adsorbent andcyclohexane as the mobile phase. Yield: 72%; colorless oil.

Intermediate 10b

1-(4-Fluorobenzyl)-cyclopropanecarboxylic acid ##STR30##

25.0 g (0.10 mol) of tert-butyl1-(4-fluoro-benzyl)-cyclopropanecarboxylate (prepared according toIntermediate 10a) were reacted with 14.3 g (0.13 mol) of trifluoroaceticacid, similarly to Intermediate 1c. Yield: 90%; colorless oil.

Example 11 (Compound No. 30 in Table 1)

2-[1-(4-Fluorobenzyl)-cyclopropylcarbonyloxymethyl]phenylglyoxylic acidmethyl ester O-methyloxime ##STR31##

A method similar to Example 2 was used and 5.8 g (30 mmol) of1-(4-fluorobenzyl)-cyclopropanecarboxylic acid (prepared according toIntermediate 10a) were converted with 1.8 g (32 mmol) of potassiumhydroxide into the potassium salt of fluorobenzylcyclopropanecarboxylicacid, and said salt was then reacted with 6.3 g (22 mmol) of2-(bromomethyl)-phenylglyoxylic acid methyl ester O-methyloxime.Purification was carried out by chromatography using silica gel as theadsorbent ant toluene as the mobile phase. Yield: 62%; colorless oil.

Example 12 (Compound No. 261 in Table 2) Methylalpha-[2-(1,2-dimethylcyclopropylcarbonyloxymethyl)-phenyl]-beta-methoxyacrylate##STR32##

A stirred solution of 3.8 g (27 mmol) of ethyl1,2-dimethylcyclopropanecarboxylate and 1.6 g (29 mmol) of potassiumhydroxide in 50 ml of ethanol was refluxed for 8 hours and thenevaporated down. The solution was covered with a layer of diethyl ether,after which the resulting precipitate was separated off and washed withdiethyl ether. Subsequent reaction of the resulting potassium salt ofdimethylcyclopropanecarboxylic acid in 60 ml of N-methylpyrrolidone, at100° C., with 4.2 g (15 mmol) of methylalpha-(2-bromomethylphenyl)-beta-methoxyacrylate and purification of theend product were carried out similarly to Example 1. Yield: 69%;colorless oil.

Intermediate 12a

Ethyl 1,2-dimethyl-3,3-dibromo-1-cyclopropanecarboxylate ##STR33##

1 g (2 mmol) of hexadecyltributylphosphonium bromide and 50 ml of 50%strength by weight aqueous sodium hydroxide solution were added to asolution of g (0.25 mol) of ethyl (E)-2-methyl-2-butenoate in 80 32 mlof methylene chloride. Thereafter, 75.6 g (0.30 mol) of bromoform wereadded dropwise at 20° C. and the reaction mixture was stirred for 24hours at 20° C. and for a further 8 hours at 50° C. 100 ml of water wasthen added to the mixture and the product was extracted with methylenechloride. The organic phase was worked up in a conventional manner toobtain the product. The crude product was purified by distillation.Yield: 37%; bp.: 102° C. 2 mbar; colorless oil.

Intermediate 12b

Ethyl 1,2-dimethylcyclopropanecarboxylate ##STR34##

55 g (0.19 mol) of tributyltin hydride was slowly added dropwise at 20°C. to a solution of 24 g (0.08 mol) of ethyl1,2-dimethyl-3,3-dibromo-1-cyclopropanecarboxylate (prepared accordingto Intermediate 12a) in 50 ml of diethyl ether. Stirring was carried outfor 12 hours at 20° C., after which the solvent was removed. The mixturewas then stirred for a further 2 hours at 140° C. and was then separatedby distillation at about 15 mbar (reduced pressure from a water pump).Yield: 76%; bp.: 54°-56° C. at 15 mbar; colorless oil.

Example 13 (Compound No. 263 in Table 2) Methyl alpha- [2-(1,2-dimethyl-3,3-dibromocyclopropylcarbonyloxymethyl) -phenyl]-beta-methoxyacrylate ##STR35##

A solution of 11.0 g (36 mmol) of ethyl1,2-dimethyl-3,3-dibromocyclopropanecarboxylate (prepared according toIntermediate 12a) and 2.2 g (40 mmol) of potassium hydroxide in 100 mlof ethanol was stirred for 6 hours at 60° C. and then evaporated down.The solution was covered with a layer of diethyl ether, after which theresulting precipitate was separated off and washed with diethyl ether.Subsequent reaction of the resulting potassium salt ofdimethyldibromocyclopropanecarboxylic acid in 60 ml ofN-methylpyrrolidone with 5.1 g (18 mmol) of methyl alpha-(2-bromomethylphenyl ) -beta-methoxyacrylate was carried out similarlyto Example 1. After hydrolysis of the reaction mixture, the product wasextracted with methyl tert-butyl ether and was isolated and purifiedsimilarly to Example 1. Yield: 32% colorless oil.

The physical data of the end products I are shown in Tables 1 to 4below, which list further compounds which were prepared, or can beprepared, by the same methods.

    TABLE 1      ##STR36##       No. R.sup.1 X Config.*.sup.) Physical data (NMR in CDCl.sub.3 [ppm];     TMS as standard)        1 H.sub.3 CCH.sub.2 CH    2 H.sub.3 CCH.sub.2 N  3 H.sub.3      CCH.sub.2CH.sub.2 CH E 62-64° C.; NMR: 0.68(m, 2H); 0.89(t, 3H);     1.20(m, 2H); 1.51(m, 4H);     3.68(s, 3H); 3.79(s, 3H); 5.00(s, 2H);     7.13-7.41(m, 4H); 7.57(s, 1H).  4 H.sub.3      CCH.sub.2CH.sub.2 N E 56-59° C.; NMR 0.68(m, 2H); 0.87(t, 3H);     1.17(m, 2H); 1.47(m, 4H);     3.87(s, 3H); 4.05(s, 3H); 4.95(s, 2H);     7.13-7.45(m, 4H).  5 H.sub.2 CCHCH.sub.2 CH E oil; NMR: 0.76(m, 2H);     1.24(m, 2H); 2.35(d, 2H); 2.69(s, 3H);     3.80(s, 3H); 5.00(s, 2H);     5.04(d, 2H); 5.85(m, 1H); 7.13-7.43(m, 4H);     7.59(s, 1H).  6 H.sub.2  C     CHCH.sub.2 N E oil; NMR: 0.73(m, 2H); 1.20(m, 2H); 2.32(d, 2H); 3.88(s,     3H);     4.03(s, 3H); 4.98(2s, 2H); 5.05(d, 2H); 5.83(m, 1H); 7.15-7.47(m     , 4H).  7 CF.sub.3 CH E 58-60° C.; NMR: 1.27(m, 2H); 1.40(m, 2H);     3.63(s, 3H); 3.70(s, 3H);     5.10(s, 2H); 7.10-7.40(m, 4H); 7.53(s,     1H).  8 (CH.sub.3).sub.3 Si CH E oil; NMR: 0.03(s, 9H); 0.76(m, 2H);     1.19(m, 2H); 3.70(s, 3H);     3.80(s, 3H); 4.99(s, 2H); 7.13-7.44(m,     4H); 7.57(s, 1H).  9 CN CH E 91-92° C.; NMR: 1.60(m, 2H); 1.67(m,     2H); 3.70(s, 3H); 3.84(s, 3H);     7.12-7.50(m, 4H); 7.60(s, 1H).  10 CN     N  11 H.sub.3 CCH.sub.2OC(O) CH E oil; NMR: 1.24(t, 3H); 1.44(s, 4H);     3.69(s, 3H);     3.80(s, 3H); 4.16(q, 4H); 5.07(s, 1H); 7.13-7.51(m,     4H); 7.59(s, 1H).  12 H.sub.3 CCH.sub.2OC(O) N  13 2-BrC.sub. 6 H.sub.4     CH E 122-123° C.; NMR: 1.22(m, 2H); 1.75(m, 2H); 3.67(s, 3H);     3.78(s, 3H); 5.00(s, 2H); 7.07-7.60(m, 8H); 7.53(s, 1H).  14 2-BrC.sub.6     H.sub.4 N E 106-107° C.; NMR: 1.20(m, 2H); 1.76(m, 2H); 3.83(s,     3H); 4.00(s, 3H);     4.96(s, 2H); 7.10-7.60(m, 8H).      15 2,4-F.sub.2C.sub.6 H.sub.3 CH E 83-84° C.; NMR: 1.19(m, 2H);     1.65(m, 2H); 3.70(s, 3H);     3.82(s, 3H); 5.00(s, 2H); 6.77-7.31(m,     7H); 7.57(s, 1H).  16 2,4-F.sub.2C.sub.6 H.sub.3 N      17 2,6-F.sub.2C.sub.6 H.sub.3 CH E 108-110° C.; NMR: 1.25(m,     2H); 1.77(m, 2H); 3.67(s, 3H);     3.80(s, 3H); 5.00(s, 2H); 6.84-7.28(m,      7H); 7.56(s, 1H).  18 2,6-F.sub.2C.sub.6 H.sub.3 N E 122-123°     C.; NMR: 1.27(m, 2H); 1.73(m, 2H); 3.87(s, 3H);     4.03(s, 3H); 4.97(s,     2H); 6.82-7.37(m, 7H).  19 2-F-6-ClC.sub.6 H.sub.3 CH E 126-127°     C.; NMR: 1.28(m, 2H); 1.80(m, 2H); 3.67(s, 3H); 3.80(s, 3H);     5.00(s,     2H); 7.92-7.25(m, 7H); 7.53(s, 1H).  20 2-F-6-ClC.sub.6 H.sub.3 N E     89-90° C.  21 2,3,6-Cl.sub.3C.sub.6 H.sub.2 CH E oil; NMR:     1.37(m, 2H); 1.96(s, 2H); 3.68(s, 3H); 3.80(s, 3H);     5.00(s, 2H);     7.09-7.39(m, 6H); 7.57(s, 1H).  22 2,3,6-Cl.sub.3C.sub.6 H.sub.2 N  23     C.sub.6 H.sub.5CH.sub.2 CH E oil; NMR: 0.78(m, 2H); 1.27(m, 2H); 2.98(s,     2H); 3.63(s, 3H);     3.70(s, 3H); 4.79(s, 2H); 7.08-7.27(m, 9H);     7.52(s, 1H).  24 C.sub.6 H.sub.5CH.sub.2 N E oil; NMR: 0.77(m, 2H);     1.23(m, 2H); 2.98(s, 2H); 3.83(s, 3H);     4.00(s, 3H); 4.93(s, 2H);     7.12-7.37(m, 9H).  25 2-FC.sub.6 H.sub.4CH.sub.2 CH  26 2-FC.sub.6     H.sub.4CH.sub.2 N  27 3-FC.sub.6 H.sub.4CH.sub.2 CH E oil  28 3-FC.sub.6     H.sub.4CH.sub.2 N E oil  29 4-FC.sub.6 H.sub.4CH.sub.2 CH E oil; NMR:     0.80(m, 2H); 1.38(m, 2H); 2.94(s, 2H); 3.68(s, 3H);     3.74(s, 3H);     4.98(s, 2H); 6.89-7.30(m, 8H); 7.53(s, 1H).  30 4-FC.sub.6      H.sub.4CH.sub.2 N E oil; NMR: 0.75(m, 2H); 1.25(m, 2H); 2.93(s, 2H);     3.83(s, 3H);     4.00(s, 3H); 4.92(s, 2H); 6.83-6.37(m, 8H).  31     2-ClC.sub.6 H.sub.4CH.sub.2 CH  32 2-ClC.sub.6 H.sub.4CH.sub.2 N  33     C     3-Cl.sub.6 H.sub.4CH.sub.2 CH E oil  34 3-ClC.sub.6 H.sub.4CH.sub.2 N E     oil  35 4-ClC.sub.6 H.sub.4CH.sub.2 CH E oil  36 4-ClC.sub.6      H.sub.4CH.sub.2 N E oil  37 2-BrC.sub.6 H.sub.4CH.sub.2 CH      38 2-BrC.sub.6 H.sub.4CH.sub.2 N  39 3-BrC.sub.6 H.sub.4CH.sub.2 CH  40     3-BrC.sub.6 H.sub.4CH.sub.2 N  41 4-BrC.sub.6 H.sub.4CH.sub.2 CH E oil     42 4-BrC.sub.6 H.sub.4CH.sub.2 N E oil  43 2-CH.sub.3C.sub.6      H.sub.4CH.sub.2  CH  44 2-CH.sub.3C.sub.6 H.sub.4CH.sub.2 N  45     3-CH.sub.3C.sub.6 H.sub.4CH.sub.2 CH E oil  46 3-CH.sub.3C.sub.6     H.sub.4CH.sub.2 N E oil  47 4-CH.sub.3C.sub.6 H.sub.4CH.sub.2 CH  48     4-CH.sub.3C.sub.6 H.sub.4CH.sub.2 N  49 2-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2 CH  50 2-CH.sub.3 OC.sub.6 H.sub.4CH.sub.2 N  51     3-CH.sub.3 OC.sub.6 H.sub.4CH.sub.2 CH  52 3-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2 N  53 4-CH.sub.3 OC.sub.6 H.sub.4CH.sub.2 CH  54     4-CH.sub.3 OC.sub.6 H.sub.4CH.sub.2 N  55 2-C.sub.2 H.sub.5 OC.sub.6     H.sub.4CH.sub.2 CH  56 2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4CH.sub.2 N  57     3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4CH.sub.2 CH  58 3-C.sub.2 H.sub.5     OC.sub.6 H.sub.4 CH.sub.2 N  59 4-C.sub.2 H.sub.5 OC.sub.6      H.sub.4CH.sub.2 CH  60 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4CH.sub.2 N  61     4-(CH.sub.3).sub.3 CC.sub.6 H.sub.4CH.sub.2 CH  62 4-(CH.sub.3).sub.3     CC.sub.6 H.sub.4CH.sub.2 N  63 2-CF.sub.3C.sub.6 H.sub.4CH.sub.2 CH  64     2-CF.sub.3C.sub.6 H.sub.4CH.sub.2 N  65 3-CF.sub.3C.sub.6      H.sub.4CH.sub.2 CH  66 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 N      67 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2 CH  68 4-CF.sub.3C.sub.6      H.sub.4CH.sub.2 N  69 2,4-F.sub.2C.sub.6 H.sub.3CH.sub.2 CH  70     2,4-F.sub.2C.sub.6 H.sub.3CH.sub.2 N  72 2,6-F.sub.2C.sub.6      H.sub.3CH.sub.2 CH  72 2,6-F.sub.2C.sub.6 H.sub.3CH.sub.2 N  73     2,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 CH  74 2,4-Cl.sub.2 C.sub.6      H.sub.3CH.sub.2 N  75 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 CH  76     2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 N  77 2-F-6-ClC.sub.6      H.sub.3CH.sub.2 CH  78 2-F-6-ClC.sub.6 H.sub.3CH.sub.2 N      79 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 CH  80 3,4-Cl.sub.2C.sub.6     H.sub.3CH.sub.2 N  81 2,3,6-Cl.sub.3C.sub.6 H.sub.2CH.sub.2 CH  82     2,3,6-Cl.sub.3C.sub.6 H.sub.2CH.sub.2 N  83 2,4-(CH.sub.3).sub.2C.sub.6     H.sub.3CH.sub.2 CH  84 2,4-(CH.sub.3).sub.2C.sub.6 H.sub.3CH.sub.2 N  85     2,6-(CH.sub.3).sub.2C.sub.6 H.sub.3CH.sub.2 CH      86 2,6-(CH.sub.3).sub.2C.sub.6 H.sub.3CH.sub.2 N      87 3,4-(CH.sub.3).sub.2C.sub.6 H.sub.3CH.sub.2 CH      88 3,4-(CH.sub.3).sub.2C.sub.6 H.sub.3CH.sub.2 N  89 2,4-(CH.sub.3     O).sub.2C.sub.6 H.sub.3CH.sub.2 CH  90 2,4-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2 N  91 2,6-(CH.sub.3 O).sub.2C.sub.6 H.sub.3CH.sub.2 CH     92 2,6-(CH.sub.3 O).sub.2C.sub.6 H.sub.3CH.sub.2 N  93 3,4-(CH.sub.3     O).sub.2C.sub.6 H.sub.3CH.sub.2 CH  94 3,4-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2 N  95 3,4-(C.sub.2 H.sub.5 O).sub.2C.sub.6      H.sub.3CH.sub.2 CH  96 3,4-(C.sub.2 H.sub.5 O).sub.2C.sub.6      H.sub.3CH.sub.2 N  97 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 CH  98     C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 N  99 2-FC.sub.6 H.sub.4CH.sub.2     CH.sub.2CH.sub.2 CH 100 2-FC.sub.6 H.sub.4CH.sub.2 CH.sub.2CH.sub.2 N     101 3-FC.sub.6 H.sub.4CH.sub.2 CH.sub.2CH.sub.2 CH 102 3-FC.sub.6        C     H.sub.4H.sub.2 CH.sub.2CH.sub.2 N 103 4-FC.sub.6 H.sub.4CH.sub.2         C     CH.sub.2H.sub.2 CH E oil; NMR: 0.67(m, 2H); 1.20(m, 2H); 1.53(m, 2H);     1.75(m, 2H);     2.55(m, 2H); 3.67(s, 3H); 3.80(s, 3H); 5.00(s, 2H);     6.90-7.38(m, 8H); 7.58(s, 1H). 104 4-FC.sub.6 H.sub.4CH.sub.2      CH.sub.2CH.sub.2 N E oil; NMR: 0.67(m, 2H); 1.18(m, 2H); 1.53(m, 2H);     1.73(m, 2H);     2.55(m, 2H); 3.85(s, 3H); 4.02(s, 3H); 4.95(s, 2H);     6.88-7.40(m, 8H). 105 2-ClC.sub.6 H.sub.4CH.sub.2 CH.sub.2CH.sub.2 CH     106 2-ClC.sub.6 H.sub.4CH.sub.2 CH.sub.2CH.sub.2 N 107 3-ClC.sub.6     H.sub.4CH.sub.2 CH.sub.2CH.sub.2 CH 108 3-ClC.sub.6 H.sub.4CH.sub.2     CH.sub.2CH.sub.2 N 109 4-ClC.sub.6 H.sub.4CH.sub.2 CH.sub.2CH.sub.2 CH E     oil 110 4-ClC.sub.6 H.sub.4CH.sub.2 CH.sub.2CH.sub.2 N E oil 111     2-BrC.sub.6 H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 112 2-BrC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 113 3-BrC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub. 2 CH 114 3-BrC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 115 4-BrC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 116 4-BrC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 117 2-CH.sub.3C.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 118 2-CH.sub.3C.sub.6                C      H.sub.4CH.sub.2H.sub.2CH.sub.2 N 119 3-CH.sub.3C.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 120 3-CH.sub.3C.sub.6                C      H.sub.4CH.sub.2H.sub.2CH.sub.2 N 121 4-CH.sub.3C.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 122 4-CH.sub.3C.sub.6                C      H.sub.4CH.sub.2H.sub.2CH.sub.2 N 123 2-CH.sub.3 OC.sub.6                C      H.sub.4CH.sub.2H.sub.2CH.sub.2 CH 124 2-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 125 3-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 126 3-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 127 4-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 128 4-CH.sub.3 OC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 129 2-C.sub.2 H.sub.5 OC.sub.6        C     H.sub.4H.sub.2CH.sub.2CH.sub.2 CH 130 2-C.sub.2 H.sub.5 OC.sub.6     H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 131 3-C.sub.2 H.sub.5 OC.sub.6     H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 132 3-C.sub.2 H.sub.5 OC.sub.6        C     H.sub.4H.sub.2CH.sub.2CH.sub.2 N 133 4-C.sub.2 H.sub.5 OC.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 134 4-C.sub.2 H.sub.5 OC.sub.6     H.sub.4CH.sub.2CH.sub.2CH.sub.2 N 135 4-(CH.sub.3).sub.3 CC.sub.6        C     H.sub.4H.sub.2CH.sub.2CH.sub.2 CH 136 4-(CH.sub.3).sub.3 CC.sub.6        C     H.sub.4H.sub.2CH.sub.2CH.sub.2 N 137 2-CF.sub.3C.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 138 2-CF.sub.3C.sub.6                C      H.sub.4CH.sub.2H.sub. 2CH.sub.2 N 139 3-CF.sub.3C.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 140 3-CF.sub.3C.sub.6                C      H.sub.4CH.sub.2H.sub.2CH.sub.2 N 141 4-CF.sub.3C.sub.6      H.sub.4CH.sub.2CH.sub.2CH.sub.2 CH 142 4-CF.sub.3C.sub.6                C      H.sub.4CH.sub.2H.sub.2CH.sub.2 N 143 2,4-F.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 144 2,4-F.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 145 2,6-F.sub.2C.sub.6                C      H.sub.3CH.sub.2H.sub.2CH.sub.2 CH 146 2,6-F.sub.2C.sub.6                C      H.sub.3CH.sub.2H.sub.2CH.sub.2 N 147 2,4-Cl.sub.2C.sub.6                C      H.sub.3CH.sub.2H.sub.2CH.sub.2 CH 148 2,4-Cl.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 149 2,6-Cl.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 150 2,6-Cl.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 151 2-F-6-ClC.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 152 2-F-6-ClC.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 153 3,4-Cl.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 154 3,4-Cl.sub.2C.sub.6      H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 155 2,3,6-Cl.sub.3C.sub.6      H.sub.2CH.sub.2CH.sub.2CH.sub.2 CH 156 2,3,6-Cl.sub.3C.sub.6      H.sub.2CH.sub.2CH.sub.2CH.sub.2 N 157 2,4-(CH.sub.3).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 158 2,4-(CH.sub.3).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 159 2,6-(CH.sub.3).sub.2C.sub.6        C     H.sub.3H.sub.2CH.sub.2CH.sub.2 CH 160 2,6-(CH.sub.3).sub.2C.sub.6        C     H.sub.3H.sub.2CH.sub.2CH.sub.2 N 161 3,4-(CH.sub.3).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 162 3,4-(CH.sub.3).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 163 2,4-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 164 2,4-(CH.sub.3 O).sub.2C.sub.6     H.sub. 3CH.sub.2CH.sub.2CH.sub.2 N 165 2,6-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 166 2,6-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 167 3,4-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 168 3,4-(CH.sub.3 O).sub.2C.sub.6     H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 169 3,4-(C.sub.2 H.sub.5      O).sub.2C.sub.6 H.sub.3CH.sub.2CH.sub.2CH.sub.2 CH 170 3,4-(C.sub.2     H.sub.5 O).sub.2C.sub.6 H.sub.3CH.sub.2CH.sub.2CH.sub.2 N 171 C.sub.6     H.sub.5CHCHCH.sub.2 CH 172 C.sub.6 H.sub.5CHCHCH.sub.2 N 173 2-FC.sub.6     H.sub.4CHCHCH.sub.2 CH 174 2-FC.sub.6      H.sub.4CHCHCH.sub.2 N 175 3-FC.sub.6 H.sub.4CHCHCH.sub.2 CH 176     3-FC.sub.6 H.sub.4CHCHCH.sub.2 N 177 E-4-FC.sub.6 H.sub.4CHCHCH.sub.2 CH     E oil; NMR: 0.77(m, 2H); 1.23(m, 2H); 2.45(d, 2H); 3.67(s, 3H);     3.77(s, 3H); 5.00(s, 2H); 6.18(m, 1H); 6.33(d, 1H);     6.92-7.42(m,     8H); 7.58(s, 1H). 178 E-4-FC.sub.6 H.sub.4CHCHCH.sub.2 N E oil; NMR:     0.78(m, 2H); 1.23(m, 2H); 2.43(d, 2H); 3.83(s, 3H);     4.03(s, 3H);     5.00(s, 2H); 6.13(m, 1H); 6.33(d, 1H); 6.927.40(m, 8H). 179 2-ClC.sub.6     H.sub.4CHCHCH.sub.2 CH 180 2-ClC.sub.6 H.sub.4CHCHCH.sub.2 N 181     3-ClC.sub.6 H.sub.4CHCHCH.sub.2 CH 182 3-ClC.sub.6 H.sub.4CHCHCH.sub.2 N     183 E-4-ClC.sub.6 H.sub.4CHCHCH.sub.2 CH E oil 184 E-4-ClC.sub.6     H.sub.4CHCHCH.sub.2 N E oil 185 2-BrC.sub.6 H.sub.4CHCHCH.sub.2 CH 186     2-BrC.sub.6 H.sub.4CHCHCH.sub.2 N 187 3-BrC.sub.6 H.sub.4CHCHCH.sub.2 CH     188 3-BrC.sub.6 H.sub.4CHCHCH.sub.2 N 189 4-BrC.sub.6 H.sub.4CHCHCH.sub.     2 CH 190 4-BrC.sub.6 H.sub.4CHCHCH.sub.2 N 191 2-CH.sub.3C.sub.6     H.sub.4CHCHCH.sub.2 CH 192 2-CH.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 N 193     3-CH.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 CH 194 3-CH.sub.3C.sub.6      H.sub.4CHCHCH.sub.2 N 195 4-CH.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 CH 196     4-CH.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 N 197 2-CH.sub.3 OC.sub.6          C      H.sub.4CHHCH.sub.2 CH 198 2-CH.sub.3 OC.sub.6 H.sub.4CHCHCH.sub.2 N 199     3-CH.sub.3 OC.sub.6 H.sub.4CHCHCH.sub.2 CH 200 3-CH.sub.3 OC.sub.6     H.sub.4CHCHCH.sub.2 N 201 4-CH.sub.3 OC.sub.6 H.sub.4CHCHCH.sub.2 CH 202     4-CH.sub.3 OC.sub.6 H.sub.4CHCHCH.sub.2 N 203 2-C.sub.2 H.sub.5 OC.sub.6     H.sub.4CHCHCH.sub.2 CH 204 2-C.sub.2 H.sub.5 OC.sub. 6      H.sub.4CHCHCH.sub.2 N 205 3-C.sub.2 H.sub.5 OC.sub.6      H.sub.4CHCHCH.sub.2 CH 206 3-C.sub.2 H.sub.5 OC.sub.6      H.sub.4CHCHCH.sub.2 N 207 4-C.sub.2 H.sub.5 OC.sub.6      H.sub.4CHCHCH.sub.2 CH 208 4-C.sub.2 H.sub.5 OC.sub.6      H.sub.4CHCHCH.sub.2 N 209 4-(CH.sub.3).sub.3 CC.sub.6      H.sub.4CHCHCH.sub.2 CH 210 4-(CH.sub.3).sub.3 CC.sub.6      H.sub.4CHCHCH.sub.2 N 211 2-CF.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 CH 212     2-CF.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 N 213 3-CF.sub.3C.sub.6            C      H.sub.4CHCHH.sub.2 CH 214 3-CF.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 N 215     4-CF.sub.3C.sub.6 H.sub.4CHCHCH.sub.2 CH 216 4-CF.sub.3C.sub.6      H.sub.4CHCHCH.sub.2 N 217 2,4-F.sub.2C.sub.6 H.sub.3CHCHCH.sub.2 CH 218     2,4-F.sub.2C.sub.6 H.sub. 3CHCHCH.sub.2 N 219 2,6-F.sub.2C.sub.6     H.sub.3CHCHCH.sub.2 CH 220 2,6-F.sub.2C.sub.6 H.sub.3CHCHCH.sub.2 N 221     2,4-Cl.sub.2C.sub.6 H.sub.3CHCHCH.sub.2 CH 222 2,4-Cl.sub.2C.sub.6     H.sub.3CHCHCH.sub.2 N 223 2,6-Cl.sub.2C.sub.6 H.sub.3CHCHCH.sub.2 CH 224     2,6-Cl.sub.2C.sub.6 H.sub.3CHCHCH.sub.2 N 225 2-F-6-ClC.sub.6            C      H.sub.3CHCHH.sub.2 CH 226 2-F-6-ClC.sub.6 H.sub.3CHCHCH.sub.2 N 227     3,4-Cl.sub.2C.sub.6 H.sub.3CHCHCH.sub.2 CH 228 3,4-Cl.sub.2C.sub.6     H.sub.3CHCHCH.sub.2 N 229 2,3,6-Cl.sub.3C.sub.6      H.sub.2CHCH.sub.2CH.sub.2 CH 230 2,3,6-Cl.sub.3C.sub.6                  C      H.sub.2CHCH.sub.2H.sub.2 N 231 2,4-(CH.sub.3).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 CH 232 2,4-(CH.sub.3).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 N 233 2,6-(CH.sub.3).sub.2 C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 CH 234 2,6-(CH.sub.3).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 N 235 3,4-(CH.sub.3).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 CH 236 3,4-(CH.sub.3).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 N 237 2,4-(CH.sub.3 O).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 CH 238 2,4-(CH.sub.3 O).sub.2C.sub.6          C      H.sub.3CHH.sub.2CH.sub.2 N 239 2,6-(CH.sub.3 O).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 CH 240 2,6-(CH.sub.3 O).sub.2C.sub.6          C      H.sub.3CHH.sub.2CH.sub.2 N 241 3,4-(CH.sub.3 O).sub.2C.sub.6      H.sub.3CHCH.sub.2CH.sub.2 CH 242 3,4-(CH.sub.3 O).sub.2C.sub.6          C      H.sub.3CHH.sub.2CH.sub.2 N 243 3,4-(C.sub.2 H.sub.5 O).sub.2C.sub.6     H.sub.3CHCH.sub.2CH.sub.2 CH 244 3,4-(C.sub.2 H.sub.5 O).sub.2C.sub.6     H.sub.3CHCH.sub.2CH.sub.2 N 245 3-BrC.sub.6 H.sub.4 CH 246 3-BrC.sub.6     H.sub.4 N 247 2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 CH 248 2-C.sub.2     H.sub.5 OC.sub.6 H.sub.4 N 249 3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 CH 250     3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 N 251 4-C.sub.2 H.sub.5 OC.sub.6     H.sub.4 CH 252 4-C.sub.2 H.sub.5 OC.sub.6      H.sub.4 N 253 2-CF.sub.3C.sub.6 H.sub.4 CH 254 2-CF.sub.3C.sub.6     H.sub.4 N 255 4-CF.sub.3C.sub.6 H.sub.4 CH 256 4-CF.sub.3C.sub.6 H.sub.4     N 257 2,4-(CH.sub.3).sub.2C.sub.6      H.sub.3 CH 258 2,4-(CH.sub.3).sub.2C.sub.6      H.sub.3 N 259 2,6-(CH.sub.3).sub.2C.sub.6      H.sub.3 CH 260 2,6-(CH.sub.3).sub.2C.sub.6    OCH.sub.3

                  TABLE 2                                                         ______________________________________                                         ##STR37##                     Ib                                                                      Physical data (NMR in CDCl.sub.3 [ppm];              No.  R.sup.2                                                                             X      Config.*.sup.)                                                                       TMS as standard)                                     ______________________________________                                        261  H     CH     E; trans                                                                             oil; NMR: 0.32(m, 1H); 1.10(d, 3H);                                           1.23(s, 3H); 1.42(m, 2H); 3.67(s, 3H);                                        3.77(s, 3H); 4.98(s, 2H); 7.10-                                               7.43(m, 4H); 7.55(s, 1H).                            262  H     N                                                                  263  Br    CH     E; trans                                                                             oil; NMR: 1.15(d, 3H); 1.37(s, 3H);                                           2.40(m, 1H); 3.70(s, 3H); 3.80(s, 3H);                                        5.08(s, 2H); 7.13-7.50(m, 4H);                                                7.50(s, 1H).                                         264  Br    N                                                                  ______________________________________                                         *.sup.) Position of the substituents at the double bond                       C(COOCH.sub.3)COCH.sub.3 (E/Z) and position of the methyl group in the        2position of the cyclopropane ring with respect to the benzyl ester group     in the 1position (cis/trans)                                             

                  TABLE 3                                                         ______________________________________                                         ##STR38##                     Ic                                                                       Physical data (NMR in CDCl.sub.3                    No.  Hal    X      Config.*.sup.)                                                                       [ppm]; TMS as standard)                             ______________________________________                                        265  Br     CH     E      oil; NMR: 1.53(d, 1H); 1.56(s, 3H);                                           2.41(d, 1H); 3.71(s, 3H); 3.81(s, 3H);                                        5.08(s, 2H); 7.15-7.43(m, 4H);                                                7.60(s, 1H).                                        266  Br     N                                                                 ______________________________________                                         *.sup.) Position of the substituents at the double bond                       C(COOCH.sub.3)XOCH.sub.3                                                 

                  TABLE 4                                                         ______________________________________                                         ##STR39##                     Id                                                                             Physical data                                                                 (NMR in CDCl.sub.3                                                     Con-   [ppm];                                        No. R.sup.3     R.sup.4  fig.*.sup.)                                                                          TMS as standard)                              ______________________________________                                        267 C.sub.6 H.sub.5                                                                           CH.sub.3  CH                                                  268 C.sub.6 H.sub.5                                                                           CH.sub.3  N                                                   269 2-FC.sub.6 H.sub.4                                                                        CH.sub.3  CH                                                  270 2-FC.sub.6 H.sub.4                                                                        CH.sub.3  N                                                   271 3-FC.sub.6 H.sub.4                                                                        CH.sub.3  CH                                                  272 3-FC.sub.6 H.sub.4                                                                        CH.sub.3  N                                                   273 4-FC.sub.6 H.sub.4                                                                        CH.sub.3  CH                                                  274 4-FC.sub.6 H.sub.4                                                                        CH.sub.3  N                                                   275 2-ClC.sub.6 H.sub.4                                                                       CH.sub.3  CH                                                  276 2-ClC.sub. 6 H.sub.4                                                                      CH.sub.3  N                                                   277 3-ClC.sub.6 H.sub.4                                                                       CH.sub.3  CH                                                  278 3-ClC.sub.6 H.sub.4                                                                       CH.sub.3  N                                                   279 4-ClC.sub.6 H.sub.4                                                                       CH.sub.3  CH                                                  280 4-ClC.sub.6 H.sub.4                                                                       CH.sub.3  N                                                   281 2-BrC.sub.6 H.sub.4                                                                       CH.sub.3  CH                                                  282 2-BrC.sub.6 H.sub.4                                                                       CH.sub.3  N                                                   283 3-BrC.sub.6 H.sub.4                                                                       CH.sub.3  CH                                                  284 3-BrC.sub.6 H.sub.4                                                                       CH.sub.3  N                                                   285 4-BrC.sub.6 H.sub.4                                                                       CH.sub.3  CH                                                  286 4-BrC.sub.6 H.sub.4                                                                       CH.sub.3  N                                                   287 2-CH.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  CH                                                  288 2-CH.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  N                                                   289 3-CH.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  CH                                                  290 3-CH.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  N                                                   291 4-CH.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  CH                                                  292  4-CH.sub.3 C.sub.6 H.sub.4                                                               CH.sub.3  N                                                   293 2-CH.sub.3 OC.sub.6 H.sub.4                                                               CH.sub.3  CH                                                  294 2-CH.sub.3 OC.sub.6 H.sub.4                                                               CH.sub.3  N                                                   295 3-CH.sub.3 OC.sub.6 H.sub.4                                                               CH.sub.3  CH                                                  296 3-CH.sub.3 OC.sub.6 H.sub.4                                                               CH.sub.3  N                                                   297 4-CH.sub.3 OC.sub.6 H.sub.4                                                               CH.sub.3  CH                                                  298 4-CH.sub.3 OC.sub.6 H.sub.4                                                               CH.sub.3  N                                                   299 2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3  CH                                                  300 2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3  N                                                   301 3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3  CH                                                  302 3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3  N                                                   303 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3  CH                                                  304 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3  N                                                   305 4-(CH.sub.3).sub.3 CC.sub. 6 H.sub.4                                                      CH.sub.3  CH                                                  306 4-(CH.sub.3).sub.3 CC.sub.6 H.sub.4                                                       CH.sub.3  N                                                   307 2-CF.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  CH                                                  308 2-CF.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  N                                                   309 3-CF.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  CH                                                  310 3-CF.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  N                                                   311 4-CF.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  CH                                                  312 4-CF.sub.3 C.sub.6 H.sub.4                                                                CH.sub.3  N                                                   313 2,4-F.sub.2 C.sub.6 H.sub.3                                                               CH.sub.3  CH                                                  314 2,4-F.sub.2 C.sub.6 H.sub.3                                                               CH.sub.3  N                                                   315 2,6-F.sub.2 C.sub.6 H.sub.3                                                               CH.sub.3  CH                                                  316 2,6-F.sub.2 C.sub.6 H.sub.3                                                               CH.sub.3  N                                                   317 2,4-Cl.sub.2 C.sub.6 H.sub.3                                                              CH.sub.3  CH                                                  318 2,4-Cl.sub.2 C.sub.6 H.sub.3                                                              CH.sub.3  N                                                   319 2,6-Cl.sub.2 C.sub.6 H.sub. 3                                                             CH.sub.3  CH                                                  320 2,6-Cl.sub.2 C.sub.6 H.sub.3                                                              CH.sub.3  N                                                   321 2-F-6-ClC.sub.6 H.sub.3                                                                   CH.sub.3  CH                                                  322 2-F-6-ClC.sub.6 H.sub.3                                                                   CH.sub.3  N                                                   323 3,4-Cl.sub.2 C.sub.6 H.sub.3                                                              CH.sub.3  CH                                                  324 3,4-Cl.sub.2 C.sub.6 H.sub.3                                                              CH.sub.3  N                                                   325 2,3,6-Cl.sub.3 C.sub.6 H.sub.2                                                            CH.sub.3  CH                                                  326 2,3,6-Cl.sub.3 C.sub.6 H.sub.2                                                            CH.sub.3  N                                                   327 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      CH.sub.3  CH                                                  328 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      CH.sub.3  N                                                   329 2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      CH.sub.3  CH                                                  330 2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      CH.sub.3  N                                                   331 3,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      CH.sub.3  CH                                                  332 3,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      CH.sub.3  N                                                   333 2,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    CH.sub.3  CH                                                  334 2,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    CH.sub.3  N                                                   335 2,6-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    CH.sub.3  CH                                                  336 2,6-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    CH.sub.3  N                                                   337 3,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    CH.sub.3  CH                                                  338 3,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    CH.sub.3  N                                                   339 3,4-(C.sub.2 H.sub.5 O).sub.2 C.sub.6 H.sub.3                                             CH.sub.3  CH                                                  340 3,4-(C.sub.2 H.sub.5 O).sub.2 C.sub.6 H.sub.3                                             CH.sub.3  N                                                   341 C.sub.6 H.sub.5                                                                           Br  CH                                                        342 C.sub.6 H.sub.5                                                                           Br  N                                                         343 2-FC.sub.6 H.sub.4                                                                        Br  CH                                                        344 2-FC.sub.6 H.sub.4                                                                        Br  N                                                         345 3-FC.sub.6 H.sub.4                                                                        Br  CH                                                        346 3-FC.sub.6 H.sub.4                                                                        Br  N                                                         347 4-FC.sub.6 H.sub.4                                                                        Br  CH                                                        348 4-FC.sub.6 H.sub.4                                                                        Br  N                                                         349 2-ClC.sub.6 H.sub.4                                                                       Br  CH                                                        350 2-ClC.sub.6 H.sub.4                                                                       Br  N                                                         351 3-ClC.sub.6 H.sub.4                                                                       Br  CH                                                        352 3-ClC.sub.6 H.sub.4                                                                       Br  N                                                         353 4-ClC.sub.6 H.sub.4                                                                       Br  CH                                                        354 4-ClC.sub.6 H.sub.4                                                                       Br  N                                                         355 2-BrC.sub.6 H.sub.4                                                                       Br  CH                                                        356 2-BrC.sub.6 H.sub.4                                                                       Br  N                                                         357 3-BrC.sub.6 H.sub.4                                                                       Br  CH                                                        358 3-BrC.sub.6 H.sub.4                                                                       Br  N                                                         359 4-BrC.sub.6 H.sub.4                                                                       Br  CH                                                        360 4-BrC.sub.6 H.sub.4                                                                       Br  N                                                         361 2-CH.sub.3 C.sub.6 H.sub.4                                                                Br  CH                                                        362 2-CH.sub.3 C.sub.6 H.sub.4                                                                Br  N                                                         363 3-CH.sub.3 C.sub.6 H.sub.4                                                                Br  CH                                                        364 3-CH.sub.3 C.sub.6 H.sub.4                                                                Br  N                                                         365  4-CH.sub.3 C.sub.6 H.sub.4                                                               Br  CH                                                        366 4-CH.sub.3 C.sub.6 H.sub.4                                                                Br  N                                                         367 2-CH.sub.3 OC.sub.6 H.sub.4                                                               Br  CH                                                        368 2-CH.sub.3 OC.sub.6 H.sub.4                                                               Br  N                                                         369 3-CH.sub.3 OC.sub.6 H.sub.4                                                               Br  CH                                                        370 3-CH.sub.3 OC.sub.6 H.sub.4                                                               Br  N                                                         371 4-CH.sub.3 OC.sub.6 H.sub.4                                                               Br  CH                                                        372 4-CH.sub.3 OC.sub.6 H.sub.4                                                               Br  N                                                         373 2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        Br  CH                                                        374 2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        Br  N                                                         375 3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        Br  CH                                                        376 3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        Br  N                                                         377 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        Br  CH                                                        378 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        Br  N                                                         379 4-(CH.sub.3).sub.3 CC.sub. 6 H.sub.4                                                      Br  CH                                                        380 4-(CH.sub.3).sub.3 CC.sub.6 H.sub.4                                                       Br  N                                                         381 2-CF.sub.3 C.sub.6 H.sub.4                                                                Br  CH                                                        382 2-CF.sub.3 C.sub.6 H.sub.4                                                                Br  N                                                         383 3-CF.sub.3 C.sub.6 H.sub.4                                                                Br  CH                                                        384 3-CF.sub.3 C.sub.6 H.sub.4                                                                Br  N                                                         385 4-CF.sub.3 C.sub.6 H.sub.4                                                                Br  CH                                                        386 4-CF.sub.3 C.sub.6 H.sub.4                                                                Br  N                                                         387 2,4-F.sub.2 C.sub.6 H.sub.3                                                               Br  CH                                                        388 2,4-F.sub.2 C.sub.6 H.sub.3                                                               Br  N                                                         389 2,6-F.sub.2 C.sub.6 H.sub.3                                                               Br  CH                                                        390 2,6-F.sub.2 C.sub.6 H.sub.3                                                               Br  N                                                         391 2,4-Cl.sub.2 C.sub.6 H.sub.3                                                              Br  CH                                                        392 2,4-Cl.sub.2 C.sub.6 H.sub.3                                                              Br  N                                                         393 2,6-Cl.sub.2 C.sub.6 H.sub.3                                                              Br  CH                                                        394 2,6-Cl.sub.2 C.sub.6 H.sub.3                                                              Br  N                                                         395 2-F-6-ClC.sub.6 H.sub.3                                                                   Br  CH                                                        396 2-F-6-ClC.sub.6 H.sub.3                                                                   Br  N                                                         397 3,4-Cl.sub.2 C.sub.6 H.sub.3                                                              Br  CH                                                        398 3,4-Cl.sub.2 C.sub.6 H.sub.3                                                              Br  N                                                         399 2,3,6-Cl.sub.3 C.sub.6 H.sub.2                                                            Br  CH                                                        400 2,3,6-Cl.sub.3 C.sub.6 H.sub.2                                                            Br  N                                                         401 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      Br  CH                                                        402 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      Br  N                                                         403 2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      Br  CH                                                        404 2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      Br  N                                                         405 3,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      Br  CH                                                        406 3,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      Br  N                                                         407 2,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    Br  CH                                                        408 2,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    Br  N                                                         409  2,6-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                   Br  CH                                                        410 2,6-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    Br  N                                                         411 3,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    Br  CH                                                        412 3,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                    Br  N                                                         413 3,4-(C.sub.2 H.sub.5 O).sub.2 C.sub.6 H.sub.3                                             Br  CH                                                        414 3,4-(C.sub.2 H.sub.5 O).sub.2 C.sub.6 H.sub.3                                             Br  N                                                         ______________________________________                                         *.sup.) Position of the substituents at the double bond                       C(COOCH.sub.3)XOCH.sub.3                                                 

USE EXAMPLES (FUNGICIDAL ACTIVITY)

The comparative substances used were ##STR40## both of which aredisclosed in DE 37 33 870 (compounds No. 71 and 364, both having an Econfiguration at the double bond).

Example 14 Activity against wheat mildew

Leaves of pot-grown wheat seedlings of the variety Fruhgold were sprayedwith 0.006 and 0.0015% strength aqueous active ingredient formulationswhich contained 80% of active ingredient (of the active ingredientsaccording to Examples 3, 4, 5, 6, 7, 15, 18 and 261 in the Tables) and20% of emulsifier, the percentages being based on dry material, and, 24hours after the spray coating had dried on, were dusted with spores ofwheat mildew (Erysiphe graminis var. tritici). The test plants were thenplaced in a greenhouse at from 20° to 22° C. and from 75 to 80% relativehumidity. After 7 days, the extent of mildew development was evaluated.

Compared with the control experiment (no treatment, 70% fungalinfestation) and the known comparative compounds A (40-50% fungalinfestation) and B (50% fungal. infestation), the treated plants showedfungal infestation of only 0-15%.

Example 15 Activity against brown rust on wheat

Leaves of pot-grown wheat seedlings of the variety Fruhgold were dustedwith spores of brown rust (Puccinia recondita). The pots were thenplaced for 24 hours at from 20° to 22° C. in a chamber with from 90 to95% relative humidity. During this time, the spores germinated and thegerm tubes penetrated the leaf tissue. The infected plants were sprayedto run-off with a 0.025% strength aqueous spray liquor which contained80% of active ingredient and 20% of emulsifier, the percentages beingbased on dry substance, and, after the spray coating had dried on, wereplaced in a greenhouse at from 20° to 22° C. and from 65 to 70% relativehumidity. After 8 days, the extent of development of rust fungus on theleaves was evaluated.

The result shows that, when used as a 0.025% strength by weight sprayliquor, active ingredients 3, 5, 7, 15, 24, 45, 103, 109, 110 and 177have a better fungicidal action (97%) than the known comparativesubstances A (33%) and B (17%).

Example 16 Activity against Pyricularia oryzae (preventive treatment)

Leaves of pot-grown rice seedlings of the variety Bahia were sprayed torun-off with aqueous emulsions which contained 80% of active ingredientand 20% of emulsifier, the percentages being based on dry substance, and24 hours later were infected with an aqueous spore suspension ofPyricularia oryzae. The test plants were then placed in conditionedchambers at from 20° to 24° C. and 95-99% relative humidity. After 6days, the extent of fungal infestation was determined.

The result shows that, when used as a 0.05% strength by weight aqueousactive ingredient formulation, active ingredients 3, 4, 5, 6, 8, 46,103, 104, 109, 177, 183 and 261 have a much better fungicidal action(98%) than the known comparative substances A (0%) and B (50%).

USE EXAMPLES (INSECTICIDAL ACTIVITY)

The insecticidal action of ortho-substituted benzyl esters ofcyclopropanecarboxylic acids I can be demonstrated by the followingexperiments:

The active ingredients were prepared as a 10% strength emulsion in amixture of 70% by weight of cyclohexanol, 20% by weight of Nekanil® LN(Lutensol PAP6, wetting agent having an emulsifying and dispersingeffect and based on ethoxylated alkylphenols) and 10% by weight ofEmulphor® EL (Emulan® EL, emulsifier based on ethoxylated fattyalcohols) and were diluted with water to give the desired concentration.

Example 17 Activity against Tetranychus telarius (red spider); contactaction

Experiment 17 a

Bush beans which were contained in pots and had formed the second pairof secondary leaves and were severely infested with the spider miteswere sprayed to run-off with aqueous active ingredient formulations ofcompound No. 29 which were of different concentrations. For thispurpose, the plants were sprayed on a turntable from all sides withabout 50 ml of the spray liquor. After 5 days in a greenhouse, thesuccess of control was determined in % by means of a microscope(binocular).

At an active ingredient concentration of 200 ppm, compound No. 29 had akill rate of from 80 to 90%. Experiment 17 b (preventive treatment)

Bush beans which were contained in pots and had formed the second pairof secondary leaves were sprayed to run-off with active ingredientformulations of compound No. 29 which were of different concentrations,similarly to Experiment 17 a. After 24 hours, the plants were infectedwith pieces of leaf which were severely infested with spider mites.

After 12 days in a greenhouse, the success of control was determined in% by means of a microscope (binocular).

At an active ingredient concentration of 40 ppm, compound No. 29 had akill rate of from 80 to 90%.

We claim:
 1. An ortho-substituted benzyl ester of acyclopropanecarboxylic acid of the formula I: ##STR41## wherein X is═N-- or ═CH--, andR¹ is cyano, trifluoromethyl, trimethylsilyl, C₃ -C₈-alkyl, C₁ -C₄ -alkoxycarbonyl, phenyl-C₁ -C₆ -alkyl or phenyl-C₃ -C₆-alkenyl, wherein each aromatic moiety may furthermore carry 1-5 halogenatoms or up to 3 of the following substituents: C₁ -C₆ -alkyl, partiallyor completely halogenated C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy,with theproviso that when R¹ is trifluoromethyl or trimethylsilyl, X is ═CH--.2. The ortho-substituted benzyl ester of a cyclopropanecarboxylic acidof the formula I as claimed in claim 1, whereinX is ═N-- or ═CH--, andR¹ is cyano, trifluoromethyl, trimethylsilyl, C₃ -C₄ -alkyl, C₁ -C₂-alkoxycarbonyl, phenyl-C₁ -C₄ -alkyl or phenyl-C₃ -C₄ -alkenyl, whereineach aromatic moiety may furthermore be monosubstituted by halogen ormethyl,with the proviso that X is ═CH-- when R¹ is trifluoromethyl ortrimethylsilyl.
 3. The ortho-substituted benzyl ester of acyclopropanecarboxylic acid of the formula I as claimed in claim 1,whereinX is ═N-- and R¹ is cyano, C₃ -C₈ -alkyl, C₁ -C₄ -alkoxycarbonyl,phenyl-C₁ -C₆ -alkyl or phenyl-C₃ -C₆ -alkenyl, wherein each aromaticmoiety may furthermore carry 1-5 halogen atoms or up to 3 of thefollowing substituents: C₁ -C₆ -alkyl, partially or completelyhalogenated C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy.
 4. The ortho-substitutedbenzyl ester of a cyclopropanecarboxylic acid of the formula I asclaimed in claim 1, whereinX is ═CH--, and R¹ is cyano, trifluoromethyl,trimethylsilyl, C₃ -C₈ -alkyl, C₁ -C₄ -alkoxycarbonyl, phenyl-C₁ -C₆-alkyl or phenyl-C₃ -C₆ -alkenyl, wherein each aromatic moiety mayfurthermore carry 1-5 halogen atoms or up to 3 of the followingsubstituents: C₁ -C₆ -alkyl, partially or completely halogenated C₁ -C₆-alkyl or C₁ -C₆ -alkoxy.
 5. The ortho-substituted benzyl ester of acyclopropanecarboxylic acid of claim 1, wherein R¹ is n-propyl and X isCH.
 6. The ortho-substituted benzyl ester of a cyclopropanecarboxylicacid of claim 1, wherein R¹ is n-propyl and X is N.
 7. Theortho-substituted benzyl ester of a cyclopropanecarboxylic acid of claim1, wherein R¹ is alkyl and X is CH.
 8. A fungicidal composition,comprising: a solid or liquid carrier and a fungicidally effectiveamount of an ortho-substituted benzyl ester of a cyclopropanecarboxylicacid of formula I as claimed in claim
 1. 9. A pesticidal composition,comprising: an inert carrier and a pesticidally effective amount of anortho-substituted benzyl ester of a cyclopropanecarboxylic acid offormula I as claimed in claim 1.